Designing New Halogen Bonding Catalysts for Asymmetric Synthesis (BEWS1_U21SF)

This exciting PhD focuses on asymmetric synthesis and the development of new chiral non-racemic supramolecular halogen bond catalysts. The research will identify and optimize a series of chiral neutral and cationic binaphthyl catalysts for the asymmetric synthesis of sought after heterocycles, pharmacophores and natural product intermediates. Honing and expanding your practical skills you will learn and fine-tune essential new techniques as well as master innovative methods in state-of-the-art organic chemistry. The application of DFT/computational chemistry (a sought after skill) and in silico testing will allow you to further refine your catalyst whilst probing its mode of action/mechanism.  

First reported over a century ago halogen bonds (XB) are the least exploited, favourable, non-covalent electrostatic interaction between polarised, electropositive halogen atoms and electronegative oxygen or nitrogen atoms. In contrast to hydrogen bond-mediated catalysis there are few XB-mediated asymmetric catalysis reactions. This PhD seeks to redress the balance developing a new suite of XB catalysts which build on our experience in chiral asymmetric catalysis and non-racemic aziridine synthesis.  

Inititiating this project we have reported preliminary results and the first example of N-fluoropyridinium triflate as an achiral ‘off the shelf’ XB catalyst or organocatalytic source of the fluoronium cation (F+)2. Building on this success subsequent work focussed on alternative achiral and optically active organic Brønsted acids catalysts which afford easy access to racemic1 or chiral non-racemic aziridines2 in excellent yields and enantioselectivities. Expanding the repertoire of chemistry associated with this PhD you will develop and generate new XB catalysts in a research area which is, still, in its infancy and where asymmetric synthesis remains an unresolved challenge. 

Funding Notes:  

This PhD project is offered on a self-funding basis.  It is open to applicants with funding or those applying to funding sources.  Details of tuition fees can be found at https://www.uea.ac.uk/about/university-information/finance-and-procurement/finance-information-for-students/tuition-fees 

A bench fee is also payable on top of the tuition fee to cover specialist equipment or laboratory costs required for the research.  Applicants should contact the primary supervisor for further information about the fee associated with the project.